Multifunctional lubricating oil additive

ABSTRACT

The N-substituted, S-aminomethyl dithiophosphates, wherein said substituent is selected from the group consisting of hydrocarbyl, hydrocarbyl-substituted amines, and hydrocarbyl-substituted succinimides, are found to function as extreme pressure agents, oxidation inhibitors and ashless dispersants in lubricating oils.

O United States Patent 11 1 [111 3,865,740

Goldschmidt Feb. 11, 1975 MULTIFUNCTIONAL LUBRICATING OIL 2,586,6562/1952 Hook et al. 252/467 x ADDITWE 2,736,707 2/1956 Morris 252/467 x3,185,643 5/1965 Lowe et al. 252/327 E [75] Inventor: AlfredGoldschmidt. El Cerri o, 3,284,354 11/1966 Tunkel et al. 252/327 ECalif. 3,324,032 6/1967 OHalloran 252/466 7 2 46. [73] Assignee: ChevronResearch Company, San 1756951 9H9 3 Dlcken 52/ 7 Francisco Cahf' PrimaryExaminer-Patrick P. Garvin [22] Filed: Feb. 14, 1973 AssistantExaminer-Andrew H, Metz [2H Appl No: 332,864 gglflffiy Ageing, ggigrm-G.IF. Magdeburger; C. J.

Related US. Application D na [63] Continuation-impart of Ser. No.255,605, May 22, [57] ABSTRACT 1972 abandoned' The N-substituted,S-aminomethyl dithiophosphates, wherein said substituent is selectedfrom the group 252/46], 2(6:(; )3n2161.54l; consisting of hydrocarbylyhYdrocarWLsubstituted [58] mid 56521111312:11111133321215; 260/3265 Famines, and hyfimarbyl-subsm-uted succinimides-w found to function asextreme pressure agents, oxida- [56] References Cited tion inhibitorsand ashless dispersants in lubricating UNITED STATES PATENTS oils.

5 Claims, No Drawings MULTIFUNCTIONAL LUBRICATING OIL ADDITIVECROSS-REFERENCE TO RELATED APPLICATION The present application is acontinuation-in-part of U.S. application Ser. No. 255,605, filed May 22,1972 and now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention Auto manufacturersreport a number of cases of extreme oil thickening have occurred incustomer service with certain engine models and crankcase oils. Theseoils, which are excellent for light-duty, stop-and-go service, oxidizedand thickened under conditions of sustained high speed, heavy loadoperations. It is not possible to properly lubricate an engine underconditions of extreme lubricating oil viscosity and as a consequenceextensive damage to the engine can occur.

Measurements show that temperatures in excess of 300F. are not uncommonoil temperatures in engines operating at high speeds under conditions ofheavy loads, as in trailer towing. 510F. can be added to oil temperatureby power consuming options such as air conditioning. Further increasesin engine operating temperatures are caused by changes in engine designto reduce exhaust emissions. For example, high temperature thermostats,reduced compressin ratio, compression spark timing, and lean air-fuelratios tend to either increase the thermal loads on the engine coolingsystem or increase the operating temperature. Oil oxidation is promotedand oil thickening is thereby accelerated by lean air-fuel ratios whichproduce blow-by gases containing high concentrations of oxides ofnitrogen. It is believed that the oil thickening problem is related tounusually high engine temperatures and resultant oxidation. The trendtoward the operation of passenger cars at higher sustained road speedsand heavier load conditions makes this a potentially serious problem inthe formulation of ashless crankcase oils.

Very little is known about the role of oil composition in oxidative oilthickening. It has been established, Lubrican'on, Vol. 57, No. 7, 1971,that certain viscosity increases in crankcase oils under high loadconditions are correlated withoil oxidation. The mechanism of oilthickening is a very complex chemical process involving primarilyoxidation and nitration of the oil. The cited reference also shows thatadditional zinc dithiophosphate, which is a commonly used oxidationinhibitor, offers little benefit towards improving the thicken ingresistance of motor oils, in some types of formulations. within thelubricant performance range of commercial interest. It is also believedthat the presence of large amounts of ash-containing basicdetergent/dispersant, which is needed for low temperature anti-sludgeperformance, fosters oxidative thickening of the crankcase oils at hightemperature.

Consequently, it is necessary to find other oxidation inhibitors anddispersants for lubricating oils which improve the antioxidantproperties of the lubricating oils as well as low temperatureanti-sludge dispersancy. These additives are preferably ashless. It isfound that a formaldehyde of condensation products of formadlehyde andcertain dithiophosphoric acid esters with certain high molecular weightamines and imides, which are hereafter described as N-substituted, S-aminomethyl dithiophosphates, form an improved class ofantioxidants/dispersants for lubricating oil compositions. TheN-substituted, S-aminomethyl dithiophos phates were also found tofunction as extreme pressure agents.

2. Description of the Prior Art US. Pat. No. 2,586,656 describes certainlow molecular weight S-aminoalkylidene dithiophosphoric acid triesterswhich may serve as antioxidant additives in lubricating oilcompositions.

SUMMARY OF THE INVENTION A class of dithiophosphoric acid esterderivatives has been found to possess a surprising lubricating additivetrifunctionality, in that they function as effective extreme pressureagents, antioxidants and ashless dispersants when present in 0.5 to 10percent by weight in lubricating oil compositions. These additives areN- substituted, S-aminomethyl dithiophosphates, wherein said substituentis selected from the group consisting of hydrocarbyl,hydrocarbyl-substituted amine, and hydrocarbyl-substituted succinimide,and said hydrocarbyl-substituents contain at least 40 carbon atoms. Theyhave the additional advantage of being ashless.

DESCRIPTION OF PREFERRED EMBODIMENTS The dithiophosphates of the presentinvention are 0,0-diesters of dithiophosphoric acid. Thesedithiophosphates are alkyl, aryl, alkaryl or aralkyl diesters ofdithiophosphoric acid. The N-substituted, S- aminomethyldithiophosphates of the present invention are derived from thedithiophosphates by concensing the 0,0-diester of dithiophosphoric acidwith formaldehyde, or another aldehyde, and a hydrocarbylsubstitutedamine, polyamine, or hydrocarbylsubstituted succinimide of a polyamine.The condensation is believed to proceed according to the followingreaction:

1 mono I-lN-X 1120 \SH it i mo n o \S-CHNX R and R are alkyl, aryl,alkaryl or aralkyl radicals, or heteroatom-substituted hydrocarbylradicals, of from low to moderate molecular weight and they may be thesame or different. The 0,0-diester of dithiophosphoric acid is producedby the reaction of phosphorus pentasulfide with an alcohol, mixture ofalcohols, or alkylphenol from which R and R are derived. R and R can bealkyl, aryl, alkaryl or aralkyl groups of from about 1 to about 20carbon atoms. R and R can also be derived from ether-cappedpolyloxyalkylene glycols. Preferably, R and R are hydrocarbyl orsubstituted hydrocarbyl groups of relatively low molecular weight, suchas methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, tetradecyl,dodecyl, decyl, octadecyl, phenyl, naphthyl, methyl phenyl, butylphenyl, isooctyl, polypropenyl, polyisobutenyl, etc.

The aldehyde which is the preferred condensing agent for the preparationof the products of this invention is formaldehyde, in which case R ishydrogen. However, formaldehyde may be replaced by other aldehydes, forexample, benzaldehyde, isobutyraldehyde, butyraldehyde, propionaldehyde,:acetaldehyde, valeraldehyde, hexaldehyde, etc., in which case R is ahydrocarbyl or substituted hydrocarbyl group.

HNXY represents a substituted primary or secondary amine of relativelyhigh molecular weight (SOD-10,000). X and Y are radicals of which onemay be hydrogen, but at least one is chosen from the group consisting ofhydrocarbyl, hydrocarbyl-substituted amine and hydrocarbyl-substitutedsuccinimide of a polyamine. Consequently, the reactant HNXY is ahydrocarbyl-substituted amine or polyamine, or a hydrocarbyl-substitutedsuccinimide of a polyamine.

Hydrocarbyl, as used herein, denotes a monovalent organic radicalcomposed of carbon and hydrogen, except for minor, insubstantial,sometimes adventitious, amounts of other elements such as oxygen,nitrogen, halogen, etc., which may be aliphatic, alicyclic, aromatic, orcombinations thereof, e.g., aralkyl. Preferably the hydrocarbyl groupwill be relatively free of aliphatic unsaturation, i.e., ethylenic andacetylenic, particularly acetylenic unsaturation.

The hydrocarbyl substituent in HNXY contains an average of at least 40and preferably less than an average of 300 carbon atoms. It ispreferably aliphatic, having preferably from zero to two sites ofethylenic unsaturation and most preferably from zero to one such site.Hydrocarbyl groups derived from a polyolefin, itself derived fromolefins (normally l-olefins) of from two to six carbon atoms (ethylenebeing copolymerized with a higher olefin), or from a higher molecularweight petroleum-derived hydrocarbon, are preferred, and of these,polyisobutene containing from 40 to about 100 carbon atoms is mostpreferred. Illustrative sources for the high molecular weighthydrocarbyl substituents are petroleum mineral oils such as naphthenicbright stocks, polypropylene, polyisobutylene, poly-l-butene, copolymersof ethylene and propylene, poly-l-pentene, poly-4-methyl-l-pentene,poly-l-hexene, poly-3- methylbutene-l, etc.

The hydrocarbyl-substituted amines are derived from lower molecularweight amines (LMW amine), preferably alkylene polyamines andpolyalkylene polyamines, by, for example, the reaction of a halogenatedhydrocarbon with the LMW amine. Examples of such LMW amines includeethylenediamine, methylamine, 2- aminoethyl piperazine, decylamine,diethylenetriamine, octadecylamine, di(trimethylene) triamine, ethylenedipiperazine, dipropylenetriamine, piperazine, triethylenetetramine,tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine,etc. The LMW amines encompass substituted and alkylsubstituted amines,e.g., N-methylethylenediamine, hydroxyethyl piperazine,N,N'-dimethylethylenediamine, N,N-dimethylpropylenediamine,N,N-dimethyldiamino propane, N-hydroxyethyl ethylenediamine, etc. Amineshaving up to about 12 amino nitrogens and up to about 36 carbon atomsare especially preferred LMW amines. The hydrocarbyl-substituted aminesare prepared, in general, by the reaction of halogenated hydrocarbonwith the LMW amine. Details of such preparations and further descriptionof certain hydrocarbyl amines can be found in Hotten and Anderson US.Pat. No. 3,565,804.

In preparing the compositions of this invention, rarely will a singlecompound be employed. With both the polymers and the petroleum-derivedhydrocarbyl groups, the composition is a mixture of materials havingvarious structures and molecular weights. Therefore, in referring tomolecular weight, average molecular weights are intended. Furthermore,when speaking of a particular hydrocarbyl group, it is intended that thegroup include the mixture that is normally contained with materialswhich are commercially available; that is, polyolefins are known to havea range of molecular weights. Furthermore, depending on the method ofpreparation, the end group of the polymer may vary and may beterminated, not only with an isobutene group, but also with a 1- or2-butene group. In addition. alkylene polyamines which are commerciallyavailable are frequently mixtures of various alkylene polyamines andbranched chain isomers having one or two species dominating. Thus, incommerically availabletetraethylene pentamine, there will also be smallamounts of pentaethylene hexamine and triethylene tetramine. Inreferring to hydrocarbyl-substituted tetraethylene pentamine, which isthe preferred amine, it is intended not only to include the purecompound, but those mixtures which are obtained with commerciallyavailable alkylene polyamines. Finally, as indicated, in preparing thecompounds of this invention, where the various nitrogen atoms of thealkylene polyamine are not equivalent, the product will be a mixture ofthe various possible isomers.

The hydrocarbyl-substituted succinimides which find use as nitrogensubstituents in the N-substituted, S- aminomethyl dithiophosphate areprepared by first making a monohydrocarbyl succinic acid or anhydridederivative and then reacting the resultant anhydride or acid with apolyamine. These compounds are described in more detail in numerousreferences in the art. See, for example, US. Pat. No. 3,219,666, as wellas US. Pat. Nos. 3,018,250; 3,087,936; 3,172,892; 3,630,902; and3,202,678.

The mono-hydrocarbyl succinic acids or anhydrides are prepared byforming the adduct of maleic anhydride with a suitable olefin polymer,chlorinated hydrocarbon, etc. This reaction proceeds upon mixing andheating ofthe components at temperatures in the range of from aboutl00-200C. The preparation of these mono-hydrocarbyl succinimides is theneffected by the reaction of, for example, mono-hydrocarbyl succinicanhydride with such LMW primary amines or polyamines containing aprimary amino nitrogen atom as ethylamine, propylamine, butylamine,tetraethylene pentamine, triethylene tetramine.

The preparation of certain of the hydrocarbylsubstituted succinimides ofuse in the present invention has been described in US. Pat. No.3,018,291 and the other cited US. Patents. In the preparation of thesesuccinimides, LMW polyalkylene polyamines having up to about 12 aminonitrogens are especially preferred. It is understood that the reactionproducts comprise amides, amine salts, and amidines, as well as theprincipal imide.

The preferred succinimides are polyisobutenyl suc cinimides prepared byreaction of a substituted succinic acid or anhydride derived from apolybutene having at least 40 carbon atoms and tetraethylene pentamineor triethylene tetramine. The succinic acid or anhydride and thepolyamine are preferably reacted in approximately equal molar ratio toobtain the succinimide product.

Method of Preparation Typically, one mol of substituted amine is dilutedwith benzene, approximately 0.9-1.1 mols of CH O are added, and stirredfor about one hour at l-l50F. Approximately 1 mol of dithiophosphoricacid is then added, and the mixture is heated for 3-5 hours at l70-190F.The product is then stripped of solvent and analyzed.

Example 1 650 g. of polyisobutenyl ethylene diamine (80 percentconcentrate in a 100 SSU at 100F. neutral oil), wherein the numberaverage molecular weight of the polyisobutenyl was 1,400 (average carbonnumber of 100), was diluted with 300 ml of benzene. 37 g. of a 37percent aqueous CH O solution was added, whereupon the temperature rosefrom 75 to 87F. The mixture was stirred one-half hour and 120 g. ofdi(isooctyl)dithiophosphoric acid was added in 100 ml. of benzene. Thetemperature rose to 107F, whereupon heat was applied and the mixture wasstirred for 5 hours at l70-l80F. 150 g. of a 100 SSU at 100F. neutralpetroleum oil was added, and the product stripped of solvent at 220F for3 minutes. Percent phosphorus, 1.04.

Example 2 700 g. of polyisobutenyl succinimide of ethylene diamine (as50 percent concentrate in 100 SSU at 100F. neutral petroleum oil),wherein the number average molecular weight of the polyisobutenyl was950, was diluted with 200 ml of benzene. 10.5 g. of paraformaldehyde wasadded and the mixture was stirred for 1 hour at l20l30F. 120 g. ofdi(isooctyl)dithiophosphoric acid was added in 50 ml. of benzene. Themixture was heated for four hours at 185F and stripped at 210F for 4minutes. Percent phosphorus, 1.1 percent.

Example 3 830 g. of a 50 percent concentrate of polyisobutenylsuccinimide of tetraethylene pentamine, wherein the number averagemolecular weight of the polyisobutenyl was 950, was diluted with 250 ml.of benzene. 8.5 grams of paraformaldehyde was added and the mixture wasstirred for one hour at 130F. 9.6 g. of a di(isooctyl)dithiophosphoricacid in 50 ml. of benzene was then added and the mixture was heated forfive hours at 190F. The product was stripped at 210F for 5 minutes.Percent phosphorus, 0.88 percent.

Example 4 Analogous to Example 3, using a bis(polypropenyl phenol)dithiophosphoric acid. Lubricant Composition The lubricating oils whichcomprise the basis for the composition of this invention are those oilyor greasy materials employed in lubrication. Examples of these materialsare natural and synthetic oils and greases made from these oils, andsynthetic oils. Synthetic oils include alkylene polymers, such aspolymers of propylene, butylene, etc., and mixtures thereof; alkyleneoxide-type polymers, e.g., alkylene oxide polymers prepared bypolymerization of alkylene oxide in the presence of water or alcohols,such as propylene oxide polymer, ethylene oxide polymer; carboxylic acidesters, such as those which are prepared by esterifying carboxylic acid,e.g., adipic acid, suberic acid, fumaric acid, etc. with alcohols suchas butyl alcohol, hexyl alcohol, pentaerythritol, etc.; polymers ofsilicon; alkylbiphenyl ethers and other ethers, etc. The base oils canbe used individually or in combinations wherever miscible or whenevermade so by use of mutual solvents. Oils of lubricating viscositygenerally have viscosities of 35-50,000 SUS at F.

The lubricating compositions of the present invention contain a majoramount of an oil of lubricating viscosity and will also contain afunctional amount, from 0.1 to 10 percent by weight, of theN-substituted, S- aminomethyl dithiophosphate of the present invention.In concentrates, the weight percent of this additive will usually rangefrom about 20 to 60 percent by weight.

In addition to the N-substituted, S-aminomethyl dithiophosphate, theselubricating compositions can also contain other lubricating oil andgrease additives such as oiliness agents, extreme pressure agents, rustinhibitors, other oxidation inhibitors, corrosion inhibitors, viscosityindex improving agents, dyes, detergents, dispersants, etc. Usually, foroils to be used in an internal combustion engine, the total amount ofthese additives will range from about 0.1-20 percent by weight, and moreusually from about 0.5-10 weight percent. The individual additives mayvary in amounts from about 0.01l0 weight percent of the totalcomposition. In concentrates, the weight percent of these additives willusually range from about 20-60 weight percent. Evaluation The Falex testresults are given in Table l. The Falex test is a test for extremepressure properties. In this test stationary vee-blocks are pressed oneither side of a rotating pin by a nutcracker arrangement of lever arms.Test specimens are immersed in a tank of test lubricant which is at aknown temperature. Loading is automatically increased until seizureoccurs. This failure point is indicated by shearing of the pin holdingthe vertical shaft. The load at shear in pounds. is taken as aquantitative measure of the extreme pressure property of the oilcomposition. Mineral oils may fail at 600-900 pounds. Oils with EPadditives will fail at l,000-2,000 pounds. The wear is determined byconducting the test at constant load and measuring the pin weight lossin milligrams.

The N-substituted, S-aminomethyl dithiophosphates have also been testedfor antiwear properties by means of the well-known 4-Ball Test. In thistest, three /z-Cliameter steel balls are clamped together and immersedin the test lubricant. A fourth ball is then rotated at about 1,800 rpmin contact with the other three balls. A 2050 kg. load is applied,forcing the rotating ball against the three stationary balls. The testis run for 60-30 minutes and the sizes of the wear scars on the threestationary balls are measured and the average scar size in millimetersreported. The smaller the scar, the greater the anti-wear properties ofthe test lubricant. These EP properties are reported in Table I and Il.Note that reference oils containing well-known EP agents give FalexShear test results of 850-],450 pounds. Similar properties are obtainedwith the additives of the present invention, but the Falex wear is muchless with the additives of the present invention. This excellent wearresult is confirmed in the 4-Ball test results given in Table ll.

TABLE I TABLE Ill-Continued Falex Falex Oxidator B Shear, Wear. Additivehrs. Additive" lbs. 5 phosphate 3 I 1. 0.7% zinc di(isooctyl)dithio- V 1phosphate 5% poly o y 5. 4.5% of the product of Example 1 5..succinimide of tetraethylene- 6 3 317,. pol b ytso utenyl succmimlde ofpemamme ethylenedianrine 0.7% of zinc 2 z n i wolyp p yd|(tsooctyhdlthlophosphate 2.3 p qy v ta a q 7. 4.5% of the product ofExample 2 5.4 polyisobutenyl succlnimlde of tetraethylenepentamine 85031.8 "see momma of Table I 3. 4.5% of the product of Example 1 1300 1.62

45% Ofthe ProdLlct of Example 2 1400 In a further heat stability test, 6percent of Example 3 O 5' 60% onhe product of Example 3 1300 L9 in a 496SSU at IOO F neutral petroleum 01] was heated for 48 hours at 300 F. Theproduct was found to have 63% PM!t Example 4 an undiminished oxidator Brating. When 4.5 percent "Percent by weight. All test lubricants contain15 mM/g P in a 496 SSU at 100F. neutral petroleum oil.

"See footnote a of Table l.

The Oxidator B test is our laboratory designation for a test measuringresistance to oxidation by means of a Dorntetype oxygen absorptionapparatus (R.W.Dornte, Oxidation of While Oils, Industrial andEngineering Chemistry, Vol. 28, p. 26, 1936). Normally, the conditionsare 1 atmosphere of pure oxygen at 340F and one reports the hours toabsorption of 1,000 ml. of 0 by 100 grams of oil. In the Oxidator B testa catalyst is used and a reference additive package is included in theoil. The catalyst is a mixture of soluble metal-naphthenates simulatingthe average metal analysis of used crankcase oils. Thus, the Oxidator Bmethod measures the response to conventional inhibitors in a simulatedapplication. The results are given in Table 111 where the composition ofthe present invention is compared to compositions containing otherdithiophosphates. Direct comparisons are made in Table III betweenAdditives l and 3, 4 and 5, and 6 and 7, which correspond to the Zinccontaining additive and the corresponding ashless antioxidant of thepresent invention. These results are uniformly outstanding in favor ofthe N-substituted, S-aminomethyl dithiophosphates.

4. 3.5% of polyisobutcnyl amine 0.7% of zinc di(isoocty1) dithioof theadditive of Example 2 in the same base oil was heated for 48 hours at300F, it was found that the infrared spectrum remained practicallyunchanged.

Table IV illustrates the detergency of the N- substituted, S-aminomethyldithiophosphates. The data refers to a severe Caterpillar diesel enginetest, run for 12 hours at 1,200 rpm, 280 brake means effective pressurein psi, water temperature of the cooling jacket is 190F, the sulfurcontent of the fuel is 0.4 percent and is input at a rate which provides6,900 BTU per minute. The base oil was a 496 SSU at F. neutral petroleumoil. In Table IV the rating of groove deposits is based on a range of0-100, 100 being completely filled grooves. The rating for land depositsis based on a range of l-800, 800 being completely black. The rating forunderhead deposits is based on a range of 0-l0, 10

being completely clean.

' TABLE IV Under- Additive Grooves Lands head 1. 6% ofthe product 3.8,0.6, 60-10-10 5.8

of Example 2 i 0.5, 0.5

2. 8% of the product 7.1, 4.0, 200-1010 7.2

of Example 3 0.6, 0.5

The N-substituted, S-aminomethyl dithiophosphates were also found to benoncorrosive towards copper and lead bearings, as well as beingantioxidants, dispersants and extreme pressure agents. The uniquepolyfunctionality of high molecular weight condensation products of thepresent invention is in sharp contrast with the low molecular weightanalogs, which, for example, cannot function as lubricating oildetergents/dispersants. It

is unusual to find polyfunctionality where each function depends on adifferent physical or chemical propdone by way of illustration only andwithout limitation of the invention. It will be apparent to thoseskilled in the art that numerous modifications and variations of theillustrative examples can be made in the practice of the inventionwithin the scope of the following claims.

I claim:

1. A lubricating composition comprising an oil of lubricating viscosityand from 0.l to 10 percent by weight of an N-substituted, S-aminomethyldithiophosphate, wherein said substituent is a hydrocarbyl-subtitutedsuccinimide of a hydrocarbyl polyamine, and wherein said hydrocarbylsubstituent contains at least 40 carbon atoms.

2. A lubricating oil composition according to claim 1, wherein saidhydrocarbyl-substituted succinimide is an imide of alkylene polyamine.

3. A lubricating oil composition according to claim 2, wherein saidhydrocarbyl group is a polypropenyl or polybutenyl substituentcontaining from 40 to about 300 carbon atoms, and said alkylenepolyamine is ethylene or propylene polyamine.

4. A lubricating oil composition according to claim wherein R and R arealkyl, aryl, alkaryl or aralkyl groups of from about one to 20 carbonatoms, and X and Y are radicals, one of which may be hydrogen, but atleast one of which is a hydrocarbyl-substituted succinimide of ahydrocarbyl polyamine, and wherein said hydrocarbyl substituent containsat least 40 carbon atoms.

1. A lubricating composition comprising an oil of lubricating viscosityand from 0.1 to 10 percent by weight of an N-substituted, S-aminomethyldithiophosphate, wherein said substituent is a hydrocarbyl-subtitutedsuccinimide of a hydrocarbyl polyamine, and wherein said hydrocarbylsubstituent contains at least 40 carbon atoms.
 2. A lubricating oilcomposition according to claim 1, wherein said hydrocarbyl-substitutedsuccinimide is an imidE of alkylene polyamine.
 3. A lubricating oilcomposition according to claim 2, wherein said hydrocarbyl group is apolypropenyl or polybutenyl substituent containing from 40 to about 300carbon atoms, and said alkylene polyamine is ethylene or propylenepolyamine.
 4. A lubricating oil composition according to claim 3 whereinsaid hydrocarbyl substituent is a polyisobutenyl group containing from40 to about 100 carbon atoms.
 5. A LUBRICATING OIL COMPOSITIONCONTAINING AN OIL OF LUBRICATING VISCOSITY AND FROM 0.1 TO 10 PERCENT BYWEIGHT OF A LUBRICATING OIL ADDITIVE OF THE GENERAL FORMULA